DE1163498B - Preparations for coloring living hair - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WWW PATENT OFFICE Internat. Class: A 61k

EDITORIAL

German class: 30 h -13/08

Number:

File number:

Registration date:

Display day:

S 73826 IV a / 30 h
May 4th 1961
1Θ? February 1964

It is known to repair living hair with the help of oxidizing dyes to dye, which consist of polyamino or oxyaminobenzene derivatives. For this is usually an aqueous solution of these products with an aqueous solution immediately before application to the hair Mixed hydrogen peroxide. This dyeing process can be used to create intense, natural-looking It has several disadvantages, which are well known in the art.

For example, the polyamino or oxyamino compounds are poorly exploited because they are only partially converted into dyes on the hair, while the remainder is oxidized in the dyebath and is lost when rinsing.

Another disadvantage is that you have two solutions immediately before application the hair must mix, otherwise the dye mixture will quickly oxidize and become much worse Delivers results.

Finally, it should be remembered that these are the most important and most frequently used Dyes can cause allergic reactions in some people, which is a very serious one Disadvantage means and requires certain precautionary measures when using. So must Before staining, preliminary tests are made to determine whether the person to be treated is opposite sensitive to the desired colorant.

Another type of coloring agent is also known, the "pre-made" coloring agent the hair is fixed in the state in which it is in the dye solution at the moment of application is located. These colorants generally do not have the disadvantages of the aforementioned type of dyes, but they have other shortcomings so that they are not widely used found in hair coloring.

Although numerous direct dyes are known for dyeing textile fibers, so far it has been very much difficult to find such dyes, also suitable for dyeing hair. In particular the most widespread azo dyes only deliver in this special field of application very mediocre results. Some of these dyes may have been used, but were found they only have very faint hues.

The invention is based on the discovery that with the help of certain direct dyes it is possible To achieve hair coloring of a quality that was previously achieved with the use of dyes of this type was unknown.

The living dye solution of the present invention for coloring living hair

Applicant:

L'Oreal, Paris
Representative:

Dipl.-Ing. Dipl.-Chem. Dr. phil. Dr. techn.
J. Reitstötter and Dr.-Ing. W. Bunte,
Patent attorneys,

Munich 15, Haydnstr. 5

Named as inventor:

! 5 Roger Charle, Soisy-Sous-Montmorency,
Robert Lantz,
Jean Gascon, Paris (France)

Claimed priority:

France of May 15, 1960 (No. 827 470)

Hair contains an azobenzene derivative in which several hydrogens of the azobenzenes are replaced by at least two Hydroxyl groups and an amino group or another hydroxyl group have been replaced. The azobenzene has the following formula:

In contrast to the azo dyes already used for hair dyeing, these dye solutions dye the hair vigorously in an environment of pH 7 or above, especially in the presence of ammonia, d. H. under the usual conditions of hair coloring. In some of the invention Staining solutions can also be used for staining at a pH below 7.

The dyes provided for the coloring solutions according to the invention can be mixed with one another or even be used in admixture with other dyes effective under the same conditions.

The staining solutions according to the invention can

weaker by dissolving the dye in water or in an aqueous solution of alkali salts Acids with a pn value between 7 and 11 can be produced. You can also use the dye in Dissolve ammonia water or alkali lye, dilute the solution with water and then add

409 509/410

if described with a substance that lowers the ρπ value, an intense green as is obtained an acid or an acidic salt, e.g. B. Sodium yellow.

bicarbonate or monosodium phosphate.

If the dye is in an alkali solution without further Example 4

Addition of an acidifying agent dissolved, must 5

the amount of alkali used in any case under Dissolve 0.5 g of 2,4,2'-trioxyazobenzene (obtained

those which are necessary for the saturation of the hydroxyl groups by coupling of diazotized o-aminophenol hydroxyl groups in the dye so that the keratin fiber to be dyed is not changed ^{with resorcinol) in 3 cm 3 of ammonia water at 22 ° Be.} and then make up to 100 cm ³ with water. Of the

The staining solution of the invention can beispiels- io _pH value of the solution is approximately 10.5. In the way the following dyes contain: 2,3,4-Trioxy- in the manner described in Example 1, an azobenzene, 3,4,5-trioxyazobenzene, 2,4,6-trioxyazo-intense reddish yellow, benzene, 2,4 is obtained , 2'-trioxyazobenzene, 2,4,4'-trioxyazo-

benzene, 2,3,4,4'-tetraoxyazobenzene, 3,4,5,4'-tetraoxy- Example 5

azobenzene, 2-amino-4,2'-dioxyazobenzene, 4-amino-15

2,2'-dioxyazobenzene, 2-amino-4,4'-dioxyazobenzene, 0.5 g of 2,4,4'-trioxyazobenzene (obtained

4-Amino-2,4'-dioxyazobenzene and 2,4,6,4-tetraoxy- azobenzene by coupling of diazotized p-aminophenol. with resorcinol) in 3 cm ³ ammonia water at 22 ° Βέ

These dyes can be raised in the usual way. The ρκ value of the solution is approximately 10.5. be made by adding a salt of diazobenzene 20 In the manner described in Example 1, or an oxydiazobenzene with a polyoxybenzene, an intense greenish yellow, derivative or mono- or polyoxyaminobenzene derivative is obtained
clutch. Example 6

In some cases this procedure will be used

Isomer mixtures obtained whose separation is desired 35 Dissolve 0.5 g of 2,4,6,4'-tetraoxyazobenzene (obtained can be. by coupling of diazotized! p-aminophenol

Some of the dyes corresponding to the general formula given above with phloroglucinol in 3 cm ³ ammonia water of formula are new. This 22 ° Be and then fill up with water to 100 cm ³ . also fall within the scope of the invention. The pH of the solution is approximately 10.5. In

The coloring solutions according to the invention can be obtained in the manner described in Example 1 In addition to the standardized derivatives of azobenzene, an intense yellow, as well as various others, in the hair dyeing technique

contain usual additives, z. B. Wetting agent, foam Example 7

substances, thickeners and swelling agents for the

Keratin fibers or substances that prevent the penetration of the 35 Man dissolve 0.5 g of a mixture of 2,3,4-trioxy dye favor. azobenzene and 3,4,5-trioxyazobenzene (obtained from

Coupling of diazotized aniline with pyrogallol)

Example Γ in 3 cm ³ ammonia water of 22 ° Be and fills

then up to 100 cm ³ with water. The pH

0.5 g of 2-amino-4,4'-dioxyazobenzene is dissolved (the solution produced is approximately 10.5. In the manner described in Example 1 by coupling diazotized p-amino, an intense green phenol is also obtained m-aminophenol) in 3 cm ^{3 of} ammonia-like yellow, water of 22 ⁰ Be and then fills up with water

100 cm ³ . The pH of the solution is approximately B eis ρ ie 1 8

10.5. Natural white hair that has not been previously dyed 45

were still permed, 1 g of 2,4,6-trioxyazobenzene in 8 cm ^{3 are stirred by one}

Brushing impregnated with this solution and rinsed after η-sodium hydroxide solution, diluted with water to 100 cm ^{3 of} exposure time for 20 minutes. Then heated to near boiling. After cooling, they are shampooed in the usual way, rinsed again with the resulting solution, whose pH value is approximately 9.1, and dried. They are intense reddish yellow if 50, it is dyed in the example 1 for dyeing. described manner. One receives a

Example 2 intense greenish yellow.

0.5 g of a mixture of 2-amino- Example 9 is dissolved

4,2'-dioxyazobenzene (produced by coupling 55

diazotized o-aminophenol with m-aminophenol) 1 g of a mixture of 2,3,4,4'-tetra is stirred

in 3 cm ^{3 of} ammonia water of 22 ° Βέ and fills up oxyazobenzene and 3,4,5,4'-tetraoxyazobenzene (hereup with water to 100 cm ^3. The ρπ value set as in Example 7) in 4 cm ^{3 of} sodium hydroxide solution , the solution is approximately 10.5. In the manner described in Example 1, diluted with water to 100 cm ³ and heated to near, an intense yellow is obtained. 60 to the boil. The cooled solution (pH approximately 9.6) is used for hair dyeing in the example 1

Example 3 used manner described. One receives a

intense greenish yellow.

Dissolve 0.5 g of 2,4,6-trioxyazobenzene (prepared

by coupling diazotized aniline with Phloro- 65 B e i s ρ i e 1 10

glucin) in 3 cm ³ ammonia water of 22 ° Be and

then make up to 100 cm ³ with water. The pn value 0.5 g of 2-amino-4,4'-dioxyazobenzene is stirred

the solution is approximately 10.5. In example 1 in 2 cm ³ η-sodium hydroxide solution, diluted with water

100 cm ³ and heated to near boiling. With the cooled solution, which has a ρπ value of approximately 9.5, the hair is treated as in the previous examples, giving it a yellow hue.

Example 11

Dissolve 0.5 g of 2,4,6-Trioxyazobenzol in 5 cm ³ m sodium hydroxide solution and then water and is 16.5 cm ³ of a 8.5% strength sodium carbonate solution ^s up to a total solution volume of 100 cm ^3. This coloring solution, the ρπ value of which is approximately 9.1, gives the hair a yellow, green color under the conditions used in the previous examples.

Example 12

Dissolve 0.5 g of 2,4,6,4'-Tetraoxyazobenzol in the cold in 4.15 cm ³ η-sodium hydroxide solution, added 8.4 cm ³ of a 10.6% i§ ^s sodium carbonate solution and 11 cm ³ of n- Hydrochloric acid is added and diluted to 100 cm ³ with water. The pH of this staining solution is approximately 8.9. With this solution, under the conditions mentioned earlier, a yellow shade is obtained on naturally white hair that was previously neither dyed nor permanently waved.

Example 13

0.5 g of 2,4,6-trioxyazobenzene is dissolved in 5 cm ^{3 of} a mixture of mono- and disodium phosphate (molar ratio 1:19) with a pa value of 8 and diluted with water to a total volume of 100 cm ³ . The staining solution obtained in this way is buffered and has a pH of 8. With their help, a yellow-green shade is obtained in the manner described earlier.

Example 14

0.5 g of 2-amino-4,4'-dioxyazobenzene is dissolved in cm ^{3 of} a solution of a mixture of sodium carbonate and sodium bicarbonate at a pH of 9 and the solution is diluted to 100 cm ³ with lukewarm water. The dye solution obtained in this way is buffered and has a pH value of approximately 9. It gives the hair a yellow color.

Claims (3)

Patent claims: 1. Colorants for living hair with a content of direct dyes, consisting of a aqueous solution of at least one azobenzene, in which several hydrogen atoms through at least two hydroxyl groups and one amino group or one further hydroxyl group are replaced. 2. Means according to claim 1, characterized in that the solution is one of the following Colorants contains: 2,3,4-trioxyazobenzene, 3,4,5-trioxyazobenzene, 2,4,6-trioxyazobenzene, 2,4,2'-trioxyazobenzene, 2,4,4'-trioxyazobenzene, 2,3,4,4'-tetraoxyazobenzene, 3,4,5,4'-tetraoxyazobenzene, 2-amino-4,2'-dioxyazobenzene, 4-amino-2,2 ' -dioxyazobenzene, 2-amino-4,4'-dioxyazobenzene, 4-amino-2,4'-dioxyazobenzene and 2,4,6,4'-tetraoxyazobenzene. 3. Means according to claim 1 or 2, characterized in that it is by means of ammonia or an alkali, in the latter case optionally with the addition of an acid or an acidic salt, is adjusted to a pH between 7 and 11. Considered publications:
German Auslegeschrift No. 1010 239;
U.S. Patent No. 2,185,467;
Austrian patent specification no.198431. When the application was announced, two staining tables were displayed. 409 509/410 2.64 © Bundesdruckerei Berlin